CN115516682A - Electrochemical device and electronic device - Google Patents
Electrochemical device and electronic device Download PDFInfo
- Publication number
- CN115516682A CN115516682A CN202180030502.7A CN202180030502A CN115516682A CN 115516682 A CN115516682 A CN 115516682A CN 202180030502 A CN202180030502 A CN 202180030502A CN 115516682 A CN115516682 A CN 115516682A
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- China
- Prior art keywords
- silicon
- equal
- electrochemical device
- present application
- negative electrode
- Prior art date
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- 239000010703 silicon Substances 0.000 claims abstract description 63
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- 239000007773 negative electrode material Substances 0.000 claims description 34
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- 239000002245 particle Substances 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 83
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 36
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The application provides an electrochemical device and electronic device, including positive pole piece, negative pole piece and electrolyte, the negative pole piece includes negative pole mass flow body and negative material layer, the negative material layer includes silica-based composite, silica-based composite includes silica-based granule, the intensity of the negative pole mass flow body is A MPa, the difference between the maximum value and the minimum value of the relative percentage content of silicon atom is B% in the silica-based granule, the mass content of silicon element is C% in the negative material layer, satisfy:
the conditions are met by cooperatively adjusting A, B and C, and the obtained lithium ion battery has good cycle performanceAnd expansion properties.
Description
Technical Field
The present application relates to the field of electrochemical technologies, and in particular, to an electrochemical device and an electronic device.
Background
Lithium ion batteries have many advantages of large volumetric and mass energy density, long cycle life, high nominal voltage, low self-discharge rate, small volume, light weight, etc., and have wide applications in the consumer electronics field. With the rapid development of electric automobiles and mobile electronic devices in recent years, people have increasingly high requirements on energy density, safety, cycle performance and other related requirements of batteries, and the appearance of novel lithium ion batteries with comprehensively improved comprehensive performance is expected.
The silicon material has high specific capacity, and can obviously improve the energy density of the lithium ion battery when being used as a negative electrode material of the lithium ion battery. However, the lithium ion battery has large volume expansion and contraction in the lithium extraction process, so that a solid electrolyte interface film (SEI) is repeatedly damaged and generated in the circulation process, reversible lithium is consumed, and the cycle performance and the expansion performance of the lithium ion battery are influenced.
Disclosure of Invention
An object of the present application is to provide an electrochemical device and an electronic device to improve cycle performance and expansion performance of a lithium ion battery. The specific technical scheme is as follows:
the first aspect of this application provides an electrochemical device, including positive pole piece, negative pole piece and electrolyte, the negative pole piece includes the negative pole mass flow body and negative material layer, wherein the negative material layer includes silica-based composite, silica-based composite includes silica-based granule, the intensity of the negative pole mass flow body is A MPa, the difference between the maximum value and the minimum value of the relative percentage content of silicon atom is B% in the silica-based granule, the mass content of elemental silicon is C% in the negative material layer, satisfies:
according to the lithium ion battery, the conditions A, B and C are adjusted in a coordinated manner, so that the lithium ion battery with good cycle performance and expansion performance can be obtained.
In one embodiment of the present application, B satisfies: b is more than or equal to 10 and less than or equal to 16. By adjusting B within the range, silicon-based particles with good silicon element distribution uniformity can be obtained, which is beneficial to reducing stress generated by expansion of the lithium ion battery, thereby obtaining the lithium ion battery with good cycle performance and expansion performance.
In one embodiment of the present application, C satisfies: c is more than or equal to 1 and less than or equal to 20. By adjusting C within the above range, the expansion performance and energy density of the lithium ion battery can be balanced.
In one embodiment of the present application, a satisfies: a is more than or equal to 370 and less than or equal to 800. By adjusting A to be within the above range, the expansion performance and the production cost of the lithium ion battery can be balanced.
In an embodiment of the present application, the single-sided thickness of the negative electrode material layer is H, and the maximum value of the particle size of the silicon-based particles is Dmax, which satisfies: h is more than or equal to 3 multiplied by Dmax. By adjusting H and Dmax to satisfy the above relationship, the cycle performance and expansion performance of the lithium ion battery can be improved.
In one embodiment of the present application, dmax of the silicon-based particles satisfies: dmax is more than or equal to 10 mu m and less than or equal to 25 mu m. By adjusting Dmax within the above range, it is advantageous to balance the processability, expansion properties, and energy density of the lithium ion battery.
In one embodiment of the present application, the single-sided thickness H of the anode material layer satisfies: h is more than or equal to 30 mu m and less than or equal to 90 mu m. By adjusting the single-side thickness H of the negative electrode material layer within the above range, the strength and toughness of the negative electrode material layer can be balanced, thereby improving the performance of the lithium ion battery.
In one embodiment of the present application, the porosity of the negative electrode sheet is P%, and P and C satisfy: p is>15×C 1/4 . By adjusting P and C to satisfy the above relationship, the expansion performance and the dynamic performance of the lithium ion battery are improved.
In one embodiment of the present application, P satisfies: p is more than or equal to 18 and less than or equal to 40. By adjusting the P within the range, the negative pole piece can be effectively soaked in the electrolyte, and has good strength, so that the expansion performance and the dynamic performance of the lithium ion battery are improved.
In one embodiment of the application, the electrolyte comprises fluoroethylene carbonate, based on the mass of the electrolyte, the fluoroethylene carbonate is in a mass percentage of Q%, and Q and C satisfy: C/Q is more than or equal to 0.3 and less than or equal to 3. By adjusting Q and C to satisfy the relationship, the lithium ion battery with good expansion performance and dynamic performance can be obtained.
In one embodiment of the present application, Q satisfies: q is more than or equal to 1 and less than or equal to 20. By adjusting Q within the range, the cycle performance of the lithium ion battery is improved.
In an embodiment of the present application, the silicon-based particles include silicon element and carbon element, and an atomic ratio of silicon to carbon in the silicon-based particles is 1: 1 to 2.5. The negative pole piece comprises the silicon-based particles with the element atomic ratio, so that the lithium ion battery with good expansion performance and cycle performance can be obtained.
A second aspect of the present application provides an electronic device comprising the electrochemical device according to the first aspect described above.
The application provides an electrochemical device and electronic device, including positive pole piece, negative pole piece and electrolyte, the negative pole piece includes negative pole mass flow body and negative electrode material layer, the negative electrode material layer includes silica-based composite, silica-based composite includes silica-based granule, the intensity of the negative pole mass flow body is A MPa, the difference between the maximum value and the minimum value of the relative percentage content of silicon atom is B% in the silica-based granule, the mass content of silicon element is C% in the negative electrode material layer, satisfy:
the conditions are met by cooperatively adjusting A, B and C, and the obtained lithium ion battery has good cycle performance and expansion performance. Of course, not all advantages described above need necessarily be achieved at the same time in the practice of any embodiment of the present application.
Drawings
In order to illustrate the technical solutions of the present application and the prior art more clearly, the following briefly introduces examples and figures that need to be used in the prior art, it being obvious that the figures in the following description are only some examples of the present application.
FIG. 1a is a cross-sectional Scanning Electron Microscope (SEM) image of a silicon-based particle;
FIG. 1b is a plot of the fluctuation in the relative percentage of silicon atoms in an X-ray energy spectrometer (EDS) line scan.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below with reference to the accompanying drawings and examples. It should be apparent that the described embodiments are only a few embodiments of the present application, and not all embodiments. All other technical solutions obtained by a person of ordinary skill in the art based on the embodiments in the present application belong to the scope of protection of the present application.
In the embodiments of the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery.
In the prior art, in order to solve the problem of lithium intercalation expansion of a silicon negative electrode, the silicon is mainly subjected to nano-crystallization and composite crystallization. For example, by reducing the grain size of the silicon material to a nanometer level, the stress generated when the silicon material is embedded with lithium is relieved, and the cracking of the material is reduced; or through the compounding of other carbonaceous materials, the contact between the carbonaceous materials and the electrolyte is reduced, and the generation of a Solid Electrolyte Interface (SEI) is reduced. However, the silicon nanocrystallization method has the problems of complex preparation process and high energy consumption, and the excessive specific surface of the nano silicon material is very easy to generate agglomeration, so that the electrical performance of the lithium ion battery is influenced; the existing composite method only aims at improvement of the carbonaceous composite material, and ignores the influence of other factors on the expansion of the lithium ion battery, so that the improvement of the expansion performance and the cycle performance of the lithium ion battery is limited. In addition, lithium intercalation leads to volume expansion which is an intrinsic property of silicon-based materials, and the scheme only can improve silicon cathode expansion to a certain extent, but is not enough to meet the application of industrial products.
In view of the above, the present application provides an electrochemical device and an electronic device to improve cycle performance and expansion performance of a lithium ion battery.
The utility model provides an electrochemical device, including positive pole piece, negative pole piece and electrolyte, the negative pole piece includes negative pole mass flow body and negative electrode material layer, wherein, the negative electrode material layer includes silica-based composite, silica-based composite includes silica-based granule, the intensity of the negative pole mass flow body is A MPa, the difference between the maximum value and the minimum value of the relative percentage content of silicon atom is B% in the silica-based granule, the mass content of silicon element is C% in the negative electrode material layer, satisfies:
the inventor of the application discovers that the difference B% between the maximum value and the minimum value of the relative percentage content of silicon atoms in the silicon-based particles is a fluctuation value, the fluctuation value can represent the uniformity degree of the distribution of silicon elements in the silicon-based particles, and the larger the fluctuation value is, the worse the uniformity degree of the distribution of the silicon elements is. The silicon undergoes volumetric expansion during intercalation, which occurs in multiple directions (e.g., along the length, width, and height directions of the lithium ion battery), and therefore the negative current collector needs to have strength to resist the stress caused by the expansion, thereby inhibiting deformation of the lithium ion battery. The inventor of the application also finds that the more uniformly the silicon element inside the silicon-based particles is distributed, the smaller the stress generated by expansion is; the more the content of the silicon element in the negative electrode material layer is, the greater the expansion tendency of the lithium ion battery in the circulating process is; with the fluctuation degree of the distribution of the silicon element in the silicon-based particles and the increase of the mass content of the silicon element in the negative electrode material layer, the requirement on the strength of the negative electrode current collector is higher, but when the negative electrode current collector exceeds a certain strength, the improvement degree of the cycle and expansion performance is greatly reduced. Based on the findings, the lithium ion battery with good cycle performance and expansion performance can be obtained by cooperatively adjusting A, B and C to meet the conditions.
In one embodiment of the present application, B satisfies: b is more than or equal to 10 and less than or equal to 16. By adjusting B within the range, silicon-based particles with good silicon element distribution uniformity can be obtained, and the stress generated by expansion of the lithium ion battery is reduced, so that the lithium ion battery with good cycle performance and expansion performance is obtained.
In one embodiment of the present application, C satisfies: c is more than or equal to 1 and less than or equal to 20. By adjusting C to be within the above range, the following can be avoided: the energy density of the lithium ion battery can be influenced by too little content of silicon element in the negative electrode material layer; the content of silicon element in the negative electrode material layer is too high, which may aggravate the expansion tendency of the lithium ion battery. Thus, by adjusting C within the above range, it is advantageous to balance the energy density and expansion performance of the lithium ion battery.
In one embodiment of the present application, a satisfies: a is more than or equal to 370 and less than or equal to 800. By adjusting a to be within the above range, the following can be avoided: the strength of the negative current collector is too low, so that the expansion performance of the lithium ion battery is influenced; the strength of the negative current collector is too high, on the one hand, the cycle and expansion performance is not improved, and on the other hand, the production cost of the current collector is greatly increased. Therefore, by adjusting a to be within the above range, it is advantageous to balance the expansion performance and production cost of the lithium ion battery.
In an embodiment of the present application, the single-sided thickness of the negative electrode material layer is H, and the maximum value of the particle size of the silicon-based particles is Dmax, which satisfies: h is more than or equal to 3 multiplied by Dmax. By adjusting H and Dmax to satisfy the above relationship, the cycle performance and expansion performance of the lithium ion battery can be improved. Presumably, this is because the silicon material intercalated lithium generates a large expansion, and when the thickness of the negative electrode plate is constant, the Dmax of the silicon-based particles is too large, which easily causes the electrode plate to expand unevenly, resulting in a local expansion of the negative electrode plate. In addition, because the negative electrode material slurry is not completely uniformly dispersed in the dispersion process, the negative electrode plate may have a condition that a part of silicon-based particles are not uniformly dispersed, and if Dmax of the silicon-based particles is too large, the negative electrode plate has bumps, which affects the appearance and performance of the negative electrode plate, and thus affects the cycle performance and expansion performance of lithium ions. Thus, by adjusting H and Dmax to satisfy the above relationship, a lithium ion battery having good cycle performance and expansion performance can be obtained.
It is understood that the negative electrode material layer may be disposed on a single side of the negative electrode current collector, i.e., coated on a single side, or disposed on both sides of the negative electrode current collector, i.e., coated on both sides. In one example, assuming that the overall thickness of the negative electrode sheet is H, the thickness of the negative electrode current collector is H1, and when double-sided coating is performed, H is: h = (H-H1)/2; when single-sided coating, then H is: h = H-H1.
In one embodiment of the present application, dmax of the silica-based particles satisfies: dmax is more than or equal to 10 mu m and less than or equal to 25 mu m. By adjusting Dmax to be within the above range, the following can be avoided: the excessive Dmax of the silicon-based particles easily causes uneven expansion of the pole pieces, and a salient point problem is easily generated in the processing process, so that the interface and the expansion performance of the lithium ion battery are influenced; the Dmax of the silicon-based particles is too small, so that the specific surface area is too large, more SEI films are generated to be accumulated on the surface of a negative electrode, the expansion tendency is increased, more binders are needed in the processing process to achieve the binding effect, and the energy density of the lithium ion battery is reduced. Therefore, the adjustment of Dmax within the above range is beneficial to balance the processability, the expansion performance and the energy density of the lithium ion battery.
In one embodiment of the present application, the single-sided thickness H of the anode material layer satisfies: h is more than or equal to 30 mu m and less than or equal to 90 mu m. By adjusting the thickness H of the single surface of the negative electrode material layer to be within the range, the strength and toughness of the negative electrode material layer can be balanced, and the performance of the lithium ion battery is improved.
In one embodiment of the present application, the porosity of the negative electrode sheet is P%, P and C satisfy: p>15×C 1/4 . By adjusting P and C to satisfy the above relationship, the expansion performance and the dynamic performance of the lithium ion battery are improved. Presumably, this is due to the fact that the silicon-based material expands very much in volume after lithium insertionThe size is large (about 300%), the problems of demolding, powder falling and the like of the negative pole piece are easily caused by a huge volume effect, and the negative pole piece with certain porosity can effectively relieve the volume expansion of the silicon-based material. However, when the porosity of the negative electrode plate is too low, the electrolyte is difficult to fully infiltrate the negative electrode plate, so that the transmission distance of lithium ions is increased, and the dynamic performance of the lithium ion battery is affected. Therefore, by adjusting P and C to satisfy the relationship, a lithium ion battery with good expansion performance and dynamic performance can be obtained.
In one embodiment of the present application, P satisfies: p is more than or equal to 18 and less than or equal to 40. By adjusting the P within the range, the negative pole piece can be effectively soaked in the electrolyte, and has good strength, so that the expansion performance and the dynamic performance of the lithium ion battery are improved.
In one embodiment of the present application, the electrolyte includes fluoroethylene carbonate (FEC), wherein the fluoroethylene carbonate is Q% by mass based on the mass of the electrolyte, and Q and C satisfy: C/Q is more than or equal to 0.3 and less than or equal to 3. By adjusting Q and C to satisfy the above relationship, the following can be avoided: when the C/Q is too high, the expansion tendency of the lithium ion battery in the cycle process is increased, and when the C/Q is too low, the mobility of lithium ions in the electrolyte is reduced due to the addition of the FEC, so that the rate capability of the lithium ion battery is influenced. Therefore, by adjusting Q and C to satisfy the relation, the lithium ion battery with good expansion performance and dynamic performance can be obtained.
In one embodiment of the present application, Q satisfies: q is more than or equal to 1 and less than or equal to 20. Fluoroethylene carbonate (FEC) is an important film forming additive in the electrolyte, and an SEI film insulating material generated by decomposition of the fluoroethylene carbonate (FEC) in the cycle process of the lithium ion battery is further contacted with the electrolyte, so that the consumption of lithium ions is reduced, and the cycle performance of the lithium ion battery is improved by adjusting Q within the range.
In an embodiment of the present application, the silicon-based particles include silicon element and carbon element, and an atomic ratio of silicon to carbon in the silicon-based particles is 1: 1 to 2.5. The negative pole piece comprises the silicon-based particles with the element atomic ratio, so that the lithium ion battery with good expansion performance and cycle performance can be obtained.
The present application is not limited to the preparation method of the silicon-based composite material, as long as the object of the present application can be achieved. For example, a porous carbon substrate is obtained by carbonizing an organic substance, and then the porous carbon substrate is subjected to heat treatment in a gas atmosphere containing silicon, thereby obtaining a silicon-based composite material. In one example, the following preparation method may be employed:
the porous carbon substrate was placed in a rotary furnace, the furnace tube was purged with nitrogen at room temperature for 20 to 40 minutes, and then the temperature of the porous carbon substrate sample was increased to 450 to 500 ℃. The nitrogen flow rate was adjusted so that the residence time of the gas in the rotary kiln was at least 90 seconds, and was maintained at this flow rate for about 30 minutes. The gas supply is then switched from nitrogen gas to a mixed gas of silicon-containing gas and nitrogen gas (the volume fraction of the silicon-containing gas in the mixed gas is 5% to 30%). After deposition for 8 to 16 hours at a gas flow rate of 200 to 400sccm, the silicon-containing gas was blown out of the rotary kiln by continuously introducing nitrogen gas into the rotary kiln, the rotary kiln was purged for 30 minutes under nitrogen gas, and then the rotary kiln was cooled to room temperature over a period of 5 to 10 hours. The silicon-based composite material is then obtained by gradually converting the nitrogen in the rotary kiln into air in 1 to 2 hours by converting the gas flow from nitrogen to air from a compressed air source.
In the present application, the kind of the porous carbon substrate is not particularly limited as long as the object of the present application can be achieved, and for example, the porous carbon substrate may be selected from at least one of hard carbon, soft carbon, and graphite. Illustratively, the hard carbon may include resin carbon, carbon black, organic polymer pyrolytic carbon, and combinations thereof. The soft carbon may include carbon fibers, carbon microspheres, and combinations thereof. The particle size of the porous carbon matrix is not limited as long as the object of the present application can be achieved. For example, the particle size range of the porous carbon matrix is 3 μm < Dv50<15 μm,15 μm < Dv99<30 μm.
The difference B% between the maximum and minimum values of the relative percentage content of silicon atoms in the silicon-based particles is related to the uniformity of the pore distribution within the carbon matrix and the pore size, e.g., the more uniform the pore distribution within the carbon matrix, the smaller the B%. Based on this, B% can be adjusted by adjusting the pore distribution and pore size.
The mass content C% of the silicon element in the anode material layer is related to the addition amount of the silicon-based composite material, wherein the content of the silicon deposited inside the silicon-based composite material can be adjusted by adjusting the deposition temperature, the deposition time and the concentration of the silicon-containing gas, for example, the C% generally increases with the increase of the deposition temperature, the C% generally increases with the increase of the deposition time and the C% generally increases with the increase of the concentration of the silicon-containing gas. Based on this, the adjustment of the mass content C% of the silicon element in the anode material layer can be performed.
The maximum value Dmax of the particle size of the silicon-based particles is in positive correlation with the particle size of the porous carbon matrix, and on the basis, the maximum value Dmax of the particle size of the silicon-based particles can be adjusted by screening the particle size of the porous carbon matrix.
The porosity of the negative pole piece is usually reduced along with the increase of the compaction density of the negative pole piece, and on the basis, the compaction density of the negative pole piece can be adjusted by adjusting the cold pressing pressure of the negative pole piece, so that the porosity of the negative pole piece is adjusted.
The atomic ratio of silicon to carbon in the silicon-based particles can be adjusted by adjusting the ratio of the silicon-containing gas to the nitrogen in the mixed gas. Generally, as the proportion of the silicon-containing gas in the mixed gas increases, more silicon element is deposited in the porous carbon matrix, so that the atomic ratio of the silicon element to the carbon element in the silicon-based particles increases.
In this application, the negative pole piece includes the negative pole current collector, and the negative pole material layer can set up on one surface or two surfaces along negative pole current collector thickness direction. The "surface" herein may be the entire region of the negative electrode current collector or a partial region of the negative electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. The negative electrode current collector is not particularly limited as long as the object of the present invention can be achieved, and for example, may include, but is not limited to, a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a composite current collector, or the like. In the present application, the thickness of the current collector of the negative electrode is not particularly limited as long as the object of the present application can be achieved, and is, for example, 4 to 12 μm. The thickness of the anode material layer of the present application may be 70 to 120 μm.
In the present application, the anode material layer may include other anode active materials known in the art in addition to the above-described silicon-based composite material, and for example, may include, but is not limited to, natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, sn, snO, and the like 2 Spinel-structured lithiated TiO 2 -Li 4 Ti 5 O 12 Or a Li-Al alloy.
In the present application, the negative electrode material layer may further include a negative electrode conductive agent, and the present application does not particularly limit the negative electrode conductive agent as long as the object of the present application can be achieved, and may include, for example, but not limited to, at least one of a carbon-based material, a metal-based material, or a conductive polymer. The carbon-based material is selected from at least one of natural graphite, artificial graphite, conductive carbon black, acetylene black, ketjen black, or carbon fiber. The metal-based material may include, but is not limited to, metal powder and/or metal fiber, and specifically, the metal may include, but is not limited to, at least one of copper, nickel, aluminum, or silver. The conductive polymer may include, but is not limited to, at least one of polyphenylene derivatives, polyaniline, polythiophene, polyacetylene, or polypyrrole.
In the present application, the negative electrode material layer may further include a negative electrode binder, and the present application does not particularly limit the negative electrode binder as long as the object of the present application can be achieved, and for example, may include, but is not limited to, at least one of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-fluoride, polyethylene, polypropylene, polyacrylic acid, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, or nylon.
Optionally, the negative electrode tab may further comprise a conductive layer, the conductive layer being located between the negative electrode current collector and the negative electrode material layer. The composition of the conductive layer is not particularly limited, and may be a conductive layer commonly used in the art, and the conductive layer may include, but is not limited to, the above-described negative electrode conductive agent and the above-described negative electrode binder.
The electrolyte of the present application may further include a lithium salt and other non-aqueous solvents, and the lithium salt is not particularly limited as long as the purpose of the present application can be achieved, and for example, may include, but is not limited to, liPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiB(C 6 H 5 ) 4 、LiCH 3 SO 3 、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 、LiC(SO 2 CF 3 ) 3 、LiSiF 6 At least one of LiBOB or lithium difluoroborate. Preferably, the lithium salt comprises LiPF 6 。
The other non-aqueous solvent is not particularly limited as long as the object of the present application can be achieved, and for example, may include, but is not limited to, at least one of carbonate compounds, carboxylate compounds, ether compounds, or other organic solvents. The carbonate compound may include, but is not limited to, at least one of a chain carbonate compound, a cyclic carbonate compound, or a fluoro carbonate compound. The above chain carbonate compound may include, but is not limited to, at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), or methylethyl carbonate (MEC). The cyclic carbonate may include, but is not limited to, at least one of Butylene Carbonate (BC) or Vinyl Ethylene Carbonate (VEC). The fluoro carbonate compound may include, but is not limited to, at least one of 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, or trifluoromethyl ethylene carbonate. The above carboxylic acid ester compound may include, but is not limited to, at least one of methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ -butyrolactone, decalactone, valerolactone, or caprolactone. The above ether compound may include, but is not limited to, at least one of dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxy-1-methoxyethane, 2-methyltetrahydrofuran, or tetrahydrofuran. The above-mentioned other organic solvent may include, but is not limited to, at least one of dimethylsulfoxide, 1, 2-dioxolane, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, or trioctyl phosphate. The content of the other non-aqueous solvent is not particularly limited as long as the object of the present application can be achieved, and for example, the content of the other non-aqueous solvent is 67% to 87% by mass, and for example, may be 67%, 67.5%, 70%, 75%, 80%, 83%, 85%, 86.5%, 87% or any range therebetween.
The electrochemical device of the present application may further include a positive electrode sheet, and the present application is not particularly limited to the positive electrode sheet as long as the purpose of the present application can be achieved, for example, the positive electrode sheet generally includes a positive current collector and a positive electrode material layer. The positive electrode material layer may be provided on one surface in the thickness direction of the positive electrode current collector, and may also be provided on both surfaces in the thickness direction of the positive electrode current collector. The "surface" herein may be the entire region of the positive electrode current collector or a partial region of the positive electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. In the present application, the positive electrode current collector is not particularly limited as long as the object of the present application can be achieved, and may include, for example, but not limited to, aluminum foil, aluminum alloy foil, or a composite current collector, etc. In the present application, the thickness of the positive electrode current collector is not particularly limited as long as the object of the present application can be achieved, and is, for example, 8 μm to 12 μm.
In the present application, the positive electrode active material is included in the positive electrode material layer, and the present application does not particularly limit the positive electrode active material as long as the object of the present application can be achieved, and for example, at least one of lithium or a composite oxide of a transition metal element may be included. The transition metal element is not particularly limited as long as the object of the present invention can be achieved, and may include at least one of nickel, manganese, cobalt, or iron, for example. Specifically, the positive active material may include at least one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate, a lithium rich manganese based material, lithium cobaltate, lithium manganese oxide, lithium manganese iron phosphate, or lithium titanate.
In the present application, the positive electrode material layer may further include a positive electrode conductive agent, and the present application does not particularly limit the positive electrode conductive agent as long as the object of the present application can be achieved, and for example, may include, but is not limited to, at least one of conductive carbon black (Super P), carbon Nanotubes (CNTs), carbon fibers, acetylene black, flake graphite, ketjen black, graphene, a metal material, or a conductive polymer, and preferably, the positive electrode conductive agent includes conductive carbon black and carbon nanotubes. The carbon nanotubes may include, but are not limited to, single-walled carbon nanotubes and/or multi-walled carbon nanotubes. The carbon fibers may include, but are not limited to, vapor Grown Carbon Fibers (VGCF) and/or carbon nanofibers. The metal material may include, but is not limited to, metal powder and/or metal fiber, and specifically, the metal may include, but is not limited to, at least one of copper, nickel, aluminum, or silver. The above-mentioned conductive polymer may include, but is not limited to, at least one of polyphenylene derivatives, polyaniline, polythiophene, polyacetylene, or polypyrrole. The positive electrode material layer may further include a positive electrode binder in the present application, and the present application is not particularly limited as long as the object of the present application can be achieved, and may include, for example, but not limited to, at least one of a fluorine-containing resin, a polypropylene resin, a fiber type binder, a rubber type binder, or a polyimide type binder.
Optionally, the positive electrode sheet may further include a conductive layer between the positive electrode current collector and the positive electrode material layer. The composition of the conductive layer is not particularly limited in the present application, and may be a conductive layer commonly used in the art, and may include, for example, but not limited to, the above-mentioned positive electrode conductive agent and the above-mentioned positive electrode binder.
The electrochemical device of the present application may further include a separation film, and the present application does not particularly limit the separation film as long as the object of the present application can be achieved. The separator may include a substrate layer and a surface treatment layer, and the present application is not particularly limited to the substrate layer, and may include, for example, but not limited to, at least one of polyethylene, polypropylene, a polyolefin-based separator mainly composed of polytetrafluoroethylene, a polyester film (e.g., polyethylene terephthalate), a cellulose film, a polyimide film, a polyamide film, spandex, an aramid film, a woven film, a non-woven film (nonwoven fabric), a microporous film, a composite film, a separator paper, a rolled film, or a spun film, preferably polyethylene or polypropylene, which have a good effect of preventing short circuits and may improve the stability of an electrochemical device by a shutdown effect. The separation membrane of the present application may have a porous structure, and the size of the pore diameter is not particularly limited as long as the object of the present application can be achieved, and for example, the size of the pore diameter may be 0.01 μm to 1 μm. In the present application, the thickness of the separator is not particularly limited as long as the object of the present application can be achieved, and for example, the thickness may be 5 μm to 500 μm.
In the present application, the surface treatment layer is not particularly limited, and may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance. The inorganic layer may include, but is not limited to, inorganic particles and an inorganic layer binder, and the inorganic particles are not particularly limited in the present application, and for example, may include, but are not limited to, at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or barium sulfate. The inorganic layer binder is not particularly limited herein, and may include, for example, but not limited to, at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, or polyhexafluoropropylene. The polymer layer includes a polymer, the polymer is not particularly limited, and the material of the polymer may include, but is not limited to, at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride, or poly (vinylidene fluoride-hexafluoropropylene).
The electrochemical device of the present application is not particularly limited, and may include any device in which electrochemical reactions occur. In some embodiments, the electrochemical device may include, but is not limited to, a lithium ion battery.
The preparation process of the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited, and for example, may include, but is not limited to, the following steps: stacking the positive pole piece, the isolating membrane and the negative pole piece in sequence, winding, folding and the like according to needs to obtain an electrode assembly with a winding structure, putting the electrode assembly into a packaging bag, injecting electrolyte into the packaging bag and sealing the packaging bag to obtain the electrochemical device; or, stacking the positive pole piece, the isolating membrane and the negative pole piece in sequence, fixing four corners of the whole lamination structure by using an adhesive tape to obtain an electrode assembly of the lamination structure, placing the electrode assembly into a packaging bag, injecting electrolyte into the packaging bag and sealing the packaging bag to obtain the electrochemical device. In addition, an overcurrent prevention element, a guide plate, or the like may be placed in the packaging bag as necessary to prevent a pressure rise or overcharge/discharge inside the electrochemical device.
A second aspect of the present application provides an electronic device comprising the electrochemical device of any one of the preceding embodiments. The electrochemical device provided by the application has good expansion performance and cycle performance, so that the electronic device provided by the application has a long service life.
The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power source, an electric motor, an automobile, a motorcycle, a moped, a bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large household battery, a lithium ion capacitor, and the like.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
The test method and the test equipment are as follows:
testing the porosity of the negative pole piece:
testing the porosity of the negative pole piece by adopting a gas displacement method: punching 50 negative pole pieces with the radius of d by adopting the same mould, measuring the thickness h of each negative pole piece, filling the 50 negative pole pieces into a sample cup of testing equipment (AccuPyc II 1340), filling the negative pole pieces by adopting helium in a closed sample bin, measuring the true volume V of the negative pole pieces, and then calculating the porosity of the negative pole pieces by adopting the following formula: p = (1-V/pi d) 2 ×50×h)×100％。
And (3) testing the strength of a current collector:
and (3) punching the current collector into a test sample with the width of 15mm and the length of 70mm by using a punching machine. And fixing the sample on a test fixture of a high-speed rail tensile machine to test the tensile strength of the sample, wherein the tensile speed is 5mm/min, and the standard distance between the two fixtures of the tensile machine is 50mm. And recording the tensile strength and displacement curve, wherein the sudden drop point of the tensile strength is the strength for resisting the damage of the external force.
And (3) testing the content of the silicon element in the negative electrode material layer:
placing the negative pole piece in a vacuum oven for drying for 24 hours at 100 ℃, scraping part of active materials on the negative pole piece by using a blade to obtain a mass M1, then placing the scraped active materials in a continuous air atmosphere for heat treatment at 800 ℃ to remove carbon materials, weighing the rest materials to obtain a mass M2, and then calculating the content of silicon elements in the negative pole material layer by the following formula: c =0.467m2/M1 × 100%.
Determination of the difference between the maximum and minimum values of the relative percentage content of silicon atoms in the silicon-based particles:
the negative electrode plate is dried in a vacuum oven at 100 ℃ for 24 hours, silicon-based particles in the plate are processed into 50nm to 100nm thin slices by Focused Ion Beam (FIB) under protective atmosphere (such as nitrogen gas), the SEM image refers to FIG. 1a, and then the relative percentage content of silicon atoms in the silicon-based particles is tested by scanning with an X-ray energy spectrometer (EDS) in a Transmission Electron Microscope (TEM) device, and the test result refers to FIG. 1b. The line scan position is selected at any position within the silicon-based particle, for example, the start point and the end point of the line scan data of fig. 1b correspond to the start point and the end point of the black arrow line of fig. 1a, and the line scan data of fig. 1b corresponds to the position where the black arrow line of fig. 1a passes through. The fluctuation value of the silicon element is the difference value between the highest value and the lowest value of the relative percentage content of the silicon atoms in the whole line sweep.
Determining the maximum value Dmax of the particle size of the silicon-based particles:
and vertically cutting the negative pole piece by adopting an ion polishing machine, randomly extracting more than 20 silicon-based particles in the pole piece under an electron microscope, testing the particle size of the silicon-based particles, and taking the maximum value of the particle size in the randomly extracted particles as Dmax.
Determination of fluoroethylene carbonate (FEC) content in electrolyte:
and (3) discharging the lithium ion battery to 0% of state of charge (SOC), centrifuging, and performing (gas chromatography mass spectrometry) GC-MS test on the centrifuged liquid to detect the mass content percentage of the FEC component in the electrolyte.
And (3) testing the normal-temperature cycle performance of the lithium ion battery:
the test temperature was 25 ℃, the lithium ion battery was charged to 4.45V at a constant current of 0.7 rate (C), then charged to 0.025C at a constant voltage, left to stand for 5 minutes and discharged to 3.0V at 0.5C. The capacity obtained in this step was used as an initial discharge capacity, and a cycle test of 0.7C charge/0.5C discharge was performed for 400 cycles, and the discharge capacity at the 400 th cycle was recorded. Cycle capacity retention ratio = (discharge capacity at 400 th cycle/discharge capacity at first cycle) × 100%.
Testing the low-temperature cycle performance of the lithium ion battery:
at 25 ℃, the formed lithium ion battery is subjected to constant current charging to 4.45V at 0.2 multiplying power (C), then is subjected to constant voltage charging until the current is less than or equal to 0.05C, then is kept stand for 30 minutes, and then is subjected to constant current discharging to 3.0V at 0.2C multiplying power, and the 0.2C multiplying power discharge capacity of the lithium ion battery at 25 ℃ is obtained through testing;
charging the lithium ion battery to 4.45V at a constant current of 0.2C multiplying power at 25 ℃, and then charging at a constant voltage until the current is less than or equal to 0.05C; and then placing the battery cell in an environment at minus 10 ℃, standing for 60 minutes, then carrying out constant current discharge at 0.2C rate to 3.0V, and testing to obtain the 0.2C rate discharge capacity of the lithium ion battery at minus 10 ℃.
Lithium ion battery-10 ℃ discharge capacity retention (%) = -10 ℃ discharge capacity at/25 ℃ discharge capacity x 100%.
Testing the expansion rate of the lithium ion battery:
the thickness of the lithium ion battery at 50% SOC was tested with a micrometer screw at a test temperature of 25 ℃ and recorded as H0, and then when cycled up to 400 cycles as in the cycle performance test, the thickness of the lithium ion battery at 100% SOC was tested and recorded as H1. Cyclic expansion rate at 25 = (H1-H0)/H0 × 100%.
Example 1-1
< preparation of silicon-based composite Material >
A porous carbon substrate having a Dmax of 25 μm was placed in a rotary kiln, the furnace tube was purged with nitrogen gas at room temperature for 30 minutes, and then the heating temperature of the porous carbon sample was raised to 450 ℃. The nitrogen flow rate was adjusted so that the residence time of the gas in the rotary kiln was at least 90 seconds and maintained at this flow rate for 30 minutes. Then, the gas supply is switched from nitrogen to a mixed gas of a silicon-containing gas (e.g., silane) and nitrogen, wherein the volume ratio of the silicon-containing gas to the nitrogen in the mixed gas is 5: 95. After 8 hours of deposition at a gas flow rate of 200sccm, the silicon-containing gas was blown out of the furnace by continuously introducing nitrogen into the rotary furnace, the rotary furnace was further purged under nitrogen for 30 minutes, and then the rotary furnace was cooled to room temperature within several hours (e.g., 8 hours). The silicon-based composite material, i.e., the silicon-based particles, was then obtained by gradually converting the nitrogen in the rotary furnace into air within 2 hours by converting the gas flow from nitrogen to air from a compressed air source. The difference B% between the maximum and minimum values of the relative percentage content of silicon atoms in the silicon-based particles was determined as shown in table 1.
< preparation of negative electrode sheet >
Mixing the prepared silicon-based composite material, graphite particles and nano conductive carbon black according to the mass ratio of 3: 94: 3 to obtain a first mixture; adding the first mixture and polyacrylic acid (PAA) as a binder into deionized water according to a mass ratio of 95: 5, blending to obtain slurry with a solid content of 70wt%, and uniformly stirring to obtain a first mixed slurry;
uniformly coating the first mixed slurry on one surface of a negative current collector copper foil with the thickness of 8 mu m, and drying for 12 hours under the conditions of vacuum drying and 85 ℃ to obtain a negative pole piece with a single-side coated with a negative active material; then, repeating the steps on the other surface of the negative pole piece to obtain the negative pole piece with the negative active material coated on the two sides; and then carrying out cold pressing, slitting and cutting on the obtained negative pole piece to obtain the negative pole piece with the specification of 76mm multiplied by 867 mm. The thickness of the negative pole piece is 90mm, and the porosity is 33%.
< preparation of Positive electrode sheet >
Mixing a positive electrode active material lithium cobaltate, conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 95: 2.5, adding NMP as a solvent, preparing slurry with the solid content of 75wt%, and uniformly stirring. And uniformly coating the slurry on one surface of an aluminum foil of the positive current collector with the thickness of 10 mu m, and drying at 90 ℃ to obtain a positive pole piece with the coating thickness of 110 mu m. And after the steps are completed, the single-side coating of the positive pole piece is completed. And then, repeating the steps on the other surface of the positive pole piece to obtain the positive pole piece with the positive active material coated on the two surfaces. Then the positive pole piece with the specification of 74mm multiplied by 851mm is obtained after cold pressing and cutting.
< preparation of electrolyte solution >
In an argon atmosphere glove box with the water content of less than 10ppm, ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) are added according to the mass ratio of 1Mixing the raw materials in a ratio of 1: 1 uniformly, adding LiPF as a basic solvent 6 Stirring uniformly to obtain electrolyte, wherein LiPF 6 The content of (b) is 12.5wt%.
< preparation of separator >
Polyethylene (PE) films (available from Celgard) with a thickness of 15 μm were used.
< preparation of lithium ion Battery >
And (3) stacking the prepared positive pole piece, the prepared isolating membrane and the prepared negative pole piece in sequence, so that the isolating membrane is positioned between the positive pole and the negative pole to play an isolating role, and winding to obtain the electrode assembly. And (3) placing the electrode assembly in an aluminum-plastic film packaging bag, drying, injecting electrolyte, and performing vacuum packaging, standing, formation, degassing, edge cutting and other processes to obtain the lithium ion battery.
Examples 1-2 to examples 1-14
The same as example 1-1 was repeated, except that the strength a of the anode current collector, the difference B between the maximum and minimum values of the relative percentage content of silicon atoms in the silicon-based particles, and the mass content C% of silicon element in the anode material layer were adjusted as shown in table 1.
Example 2-1 to example 2-9
Examples 1 to 6 were repeated except that the thickness H of one surface of the negative electrode material layer and the maximum value Dmax of the particle diameter of the silicon-based particles were adjusted as shown in table 2.
Example 3-1 to example 3-9
The examples were conducted in the same manner as in examples 2 to 3 except that the porosity P% of the negative electrode sheet was adjusted and the mass content C% of silicon element in the negative electrode material layer was adjusted as shown in table 3.
Example 4-1
The examples were conducted in the same manner as in example 1-1 except that < preparation of electrolyte > was different from example 1-1.
< preparation of electrolytic solution >
In an argon atmosphere glove box with the water content of less than 10ppm, ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) are uniformly mixed according to the mass ratio of 1: 1 to be used as a basic solvent, and LiPF is added 6 And fluoroethylene carbonate, stirring uniformly to obtain an electrolyte, wherein LiPF 6 The content of (D) is 12.5wt%, and the content of fluoroethylene carbonate is shown in Table 4.
Example 4-2 to example 4-4
The procedure was repeated in the same manner as in example 4-1 except that the amount of fluoroethylene carbonate was adjusted to Q% in percentage by mass as shown in Table 4.
Comparative examples 1-1 to 1-4
The same as in example 1-1 was repeated, except that the strength a of the negative electrode current collector, the difference B between the maximum and minimum values of the relative percentage content of silicon atoms in the silicon-based particles, and the mass content C% of silicon element in the negative electrode material layer were adjusted as shown in table 1.
TABLE 1
As can be seen from examples 1-1 to 1-14 and comparative examples 1-1 to 1-4, when the strength a of the negative electrode current collector, the difference B% between the maximum value and the minimum value of the relative percentage content of silicon atoms in the silicon-based particles, and the mass content C% of silicon element in the negative electrode material layer satisfy:
TABLE 2
The single-side thickness H of the negative electrode material layer and the maximum value Dmax of the particle size of the silicon-based particles can also influence the performance of the lithium ion battery. As can be seen from examples 1-6, 2-1 to 2-9, the lithium ion battery has good cycle performance and expansion performance when H and Dmax satisfy H.gtoreq.3XDmax.
TABLE 3
The porosity P% of the negative pole piece and the mass content C% of the silicon element in the negative pole material layer can also influence the performance of the lithium ion battery under the synergistic effect. As can be seen from examples 2-3, 3-1 to 3-9, when P and C satisfy: p>15×C 1/4 And meanwhile, the lithium ion battery has good normal-temperature cycle performance, expansion performance and low-temperature cycle performance.
TABLE 4
The mass content C% of the silicon element in the negative electrode material layer and the content Q% of the fluoroethylene carbonate in the electrolyte also influence the performance of the lithium ion battery under the synergistic effect. As can be seen from examples 3-5, 4-1 to 4-4, when Q and C satisfy: when C/Q is more than or equal to 0.3 and less than or equal to 3, the lithium ion battery has good normal-temperature cycle performance, expansion performance and low-temperature cycle performance.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (13)
1. An electrochemical device comprises a positive pole piece, a negative pole piece and electrolyte, wherein the negative pole piece comprises a negative current collector and a negative material layer,
the negative electrode material layer comprises a silicon-based composite material, the silicon-based composite material comprises silicon-based particles, the strength of the negative electrode current collector is A MPa, the difference value between the maximum value and the minimum value of the relative percentage content of silicon atoms in the silicon-based particles is B%, the mass content of silicon elements in the negative electrode material layer is C%, and the requirements are met:
2. the electrochemical device of claim 1, wherein B satisfies: b is more than or equal to 10 and less than or equal to 16.
3. The electrochemical device of claim 1, wherein C satisfies: c is more than or equal to 1 and less than or equal to 20.
4. The electrochemical device of claim 1, wherein a satisfies: a is more than or equal to 370 and less than or equal to 800.
5. The electrochemical device according to claim 1, wherein the negative electrode material layer has a single-sided thickness of H, and the maximum particle size of the silicon-based particles is Dmax, which satisfies: h is more than or equal to 3 multiplied by Dmax.
6. The electrochemical device according to claim 5, wherein the Dmax satisfies: dmax is more than or equal to 10 mu m and less than or equal to 25 mu m.
7. The electrochemical device of claim 5, wherein H satisfies: h is more than or equal to 30 mu m and less than or equal to 90 mu m.
8. The electrochemical device of claim 1, wherein the porosity of the negative electrode sheet is P%, and P and C satisfy: p is>15×C 1/4 。
9. The electrochemical device of claim 1, wherein P satisfies: p is more than or equal to 18 and less than or equal to 40.
10. The electrochemical device according to claim 1, wherein the electrolyte comprises fluoroethylene carbonate, based on the mass of the electrolyte, the fluoroethylene carbonate is present in a mass percentage of Q%, and Q and C satisfy: C/Q is more than or equal to 0.3 and less than or equal to 3.
11. The electrochemical device of claim 10, wherein Q satisfies: q is more than or equal to 1 and less than or equal to 20.
12. The electrochemical device according to claim 1, wherein the silicon-based particles comprise silicon and carbon, and an atomic ratio of silicon to carbon in the silicon-based particles is 1: 1 to 2.5.
13. An electronic device comprising the electrochemical device according to any one of claims 1 to 12.
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